Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/514—Oriented
  • B32B2307/518—Oriented bi-axially
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/75—Printability
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2519/00—Labels, badges
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S428/00—Stock material or miscellaneous articles
  • Y10S428/91—Product with molecular orientation
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
  • Y10T428/2495—Thickness [relative or absolute]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
  • Y10T428/2495—Thickness [relative or absolute]
  • Y10T428/24967—Absolute thicknesses specified
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
  • Y10T428/2495—Thickness [relative or absolute]
  • Y10T428/24967—Absolute thicknesses specified
  • Y10T428/24975—No layer or component greater than 5 mils thick
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
  • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
  • Y10T428/264—Up to 3 mils
  • Y10T428/265—1 mil or less
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
  • Y10T428/31565—Next to polyester [polyethylene terephthalate, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
  • Y10T428/31616—Next to polyester [e.g., alkyd]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31652—Of asbestos
  • Y10T428/31667—Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31678—Of metal
  • Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
  • Y10T428/31797—Next to addition polymer from unsaturated monomers

Definitions

• the invention relates to a biaxially oriented polyester film with a base layer, the consists of at least 70 wt .-% of a thermoplastic polyester, the contains at least one UV stabilizer and a flame retardant and at least a matt top layer, which is a mixture or blend of two components I and II contains.
• the invention further relates to a method for producing the Foil and its use.
• Component I of the mixture or blend is a polyethylene terephthalate homopolymer or polyethylene terephthalate copolymer or a mixture of Polyethylene terephthalate homo- or copolymers.
• Component II of the mixture or blend is a polyethylene terephthalate copolymer, which from the condensation product of the following monomers or whose derivatives are capable of forming polyesters: isophthalic acid, aliphatic dicarboxylic acid, Suffomonomeres, which has a metal sulfonate group on the contains aromatic part of an aromatic dicarboxylic acid and aliphatic or cycloaliphatic glycol.
• the top layer according to the invention is characterized by a characteristic matt Surface or optics and is for use in exhibition stand construction, in greenhouses or well suited for applications in the industrial sector where in particular UV protection or non-permeability of the UV light and flame retardancy according to DIN 4102 part 2, building material class B2 and B1.
• transparent, high-gloss plastic films such as. biaxially oriented polypropylene or biaxially oriented polyester films.
• transparent films which are flame retardant according to DIN 4102 and which have at least one surface layer is not high gloss but is characterized by a characteristic matt Distinguishes appearance and thereby e.g. a special application attractive and therefore effective advertising and protection against UV radiation, with low flammability, gives.
• a coextruded biaxially oriented polyester film which consists of a transparent base layer and at least one matt layer, which consists essentially of a certain polyethylene terephthalate copolymer and also internal particles with a diameter of 0.3 to 20 microns in one Contains a concentration of 3 to 40%.
• the special copolymer is a processing aid which lowers the viscosity of the melt containing the inner particles, so that a perfect extrusion of this layer is possible.
• the mattness of the film is achieved by adding the inner particles to the corresponding layer.
• EP 0 144 978 describes a self-supporting oriented film made of thermoplastic material, which has a continuous polyester coating on at least one of its two surfaces, which is applied as an aqueous dispersion to the film before the last stretching step.
• the polyester coating consists of a condensation product of various monomers, which consists of derivatives capable of forming polyesters, such as isophthalic acid, aliphatic dicarboxylic acid, sulfomonomers and aliphatic or cycloaliphatic glycols.
• EP-A-0 620 245 describes films which have improved thermal stability. These films contain antioxidants which are suitable for trapping radicals formed in the film and decomposing the peroxide formed.
• the object of the present invention was therefore to provide a coextruded biaxial oriented and transparent polyester film with at least one matt top layer
• the good ones has physical properties of the known films, no disposal problems caused and in particular by the absorption of UV light and due to its high UV stability and flame retardancy according to DIN 4102 and does not distinguish embrittlement after temperature exposure.
• the task is solved by a co-extruded and biaxially oriented polyester film the genus mentioned at the outset, the distinguishing features of which are that the film has at least one UV stabilizer and at least one flame retardant contains, the flame retardant and optionally the UV stabilizer Masterbatch technology can be metered in and has a matt top layer contains a mixture or a blend of two components I and II.
• Component I of the mixture or blend is a polyethylene terephthalate homopolymer or polyethylene terephthalate copolymer or a mixture of Polyethylene terephthalate homo- or copolymers.
• High UV stability means that the films are exposed to sunlight or other UV radiation not or only extremely little damage, so that the films for Outdoor applications and / or critical indoor applications are suitable.
• the foils should not yellow during several years of outdoor use, none Show embrittlement or cracking of the surface and also no deterioration of mechanical properties.
• High UV stability means therefore that the film absorbs UV light and light only in the visible range pass through.
• the good mechanical properties include a high modulus of elasticity (E MD > 3200 N / mm 2 ; E TD > 3500 N / mm 2 ) and good tensile strength values (in MD> 100 N / mm 2 ; in TD> 130 N) / mm 2 ).
• Good stretchability means that the film can be manufactured both in Longitudinal and transverse directions can be oriented excellently and without breaks.
• the economic production includes that the raw materials or the raw material components, which are needed to produce the flame retardant film with usual industrial dryers can be dried. It is essential that the Raw materials are not awarded and are not thermally broken down.
• these industrial dryers according to the prior art include vacuum dryers, fluidized bed dryers, Fluid bed dryer and fixed bed dryer (shaft dryer). These dryers work at temperatures between 100 and 170 ° C, where conventional flame retardant glue equipped raw materials and finally be mined must, so that film production is not possible.
• the most beautiful drying vacuum dryer the raw material usually passes through a temperature range from approx. 30 ° C to 130 ° C at a negative pressure of 50 mbar. After that is one So-called drying in a hopper at temperatures of 100 - 130 ° C and one Residence time of 3 to 6 hours required. Even here the known ones stick together Extreme raw materials.
• a blend in the sense of the present invention is an alloy-like composite of individual components I and II, which are no longer in the original components can be disassembled.
• a blend has properties like a homogeneous substance and can be characterized accordingly by suitable parameters.
• the UV stabilizer and the flame retardant in the top layer (s) and / or the Base layer may be included.
• the base layer B of the film preferably consists of at least 70% by weight of a thermoplastic polyester.
• polyesters which consist of at least 90 mol%, preferably at least 95 mol%, of ethylene glycol and terephthalic acid units or of ethylene glycol and naphthalene-2,6-dicarboxylic acid units.
• the remaining monomer units come from other aliphatic, cycloaliphatic or aromatic diols or dicarboxylic acids.
• Suitable other aliphatic diols are, for example, diethylene glycol, triethylene glycol, aliphatic glycols of the general formula HO- (CH 2 ) n -OH, where n represents an integer from 3 to 6 (in particular propane-1,3-diol, butane-1,4) diol, pentane-1,5-diol and hexane-1,6-diol) or branched aliphatic glycols with up to 6 carbon atoms.
• cyclohexanediols in particular cyclohexane-1,4-diol
• cyclohexanediols in particular cyclohexane-1,4-diol
• Suitable other aromatic diols correspond, for example, to the formula HO-C 6 H 4 -XC 6 H 4 -OH, where X is -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -O -, -S- or -SO 2 - stands.
• bisphenols of the formula HO-C 6 H 4 -C 6 H 4 -OH are also very suitable.
• aromatic dicarboxylic acids are preferably benzenedicarboxylic acids, naphthalenedicarboxylic acids (for example naphthalene-1,4- or 1,6-dicarboxylic acid), biphenylx, x'-dicarboxylic acids (in particular biphenyl-4,4'-dicarboxylic acid), diphenylacetylene-x, x'dicarboxylic acids (in particular diphenylacetylene-4,4'-dicarboxylic acid) or stilbene-x, x'dicarboxylic acids.
• cyclohexanedicarboxylic acids (in particular cyclohexane-1,4-dicarboxylic acid) should be mentioned.
• aliphatic dicarboxylic acids the (C 3 -C 19 ) alkanedioic acids are particularly suitable, the alkane fraction being straight-chain or branched.
• the production of the polyesters can e.g. after the transesterification process.
• This is based on dicarboxylic esters and diols, which are used with the usual Transesterification catalysts, such as zinc, calcium, lithium, magnesium and manganese salts, be implemented.
• Transesterification catalysts such as zinc, calcium, lithium, magnesium and manganese salts
• the intermediates then become general in the presence conventional polycondensation catalysts, such as antimony trioxide or titanium salts, polycondensed.
• Production can also be carried out using the direct esterification process take place in the presence of polycondensation catalysts. You go directly from the dicarboxylic acids and the diols.
• At least one cover layer of the multilayer film according to the invention contains an im following described mixture or a blend of two components I and II and any additives added.
• Component I of the top layer mixture or blend essentially contains a thermoplastic polyester, in particular such a polyester as for the Base layer was described in more detail. It has been used to produce high degrees of mattness proved to be favorable if the polyester polymer for component I of top layer according to the invention has a relatively low viscosity per se having. A modified one is used to describe the viscosities of the melts Solvent viscosity (SV value or "standard viscosity"). For commercial ones. Polyethylene terephthalates, which are suitable for the production of biaxially oriented films, the SV values are in the range from 500 to 1200.
• the total acid equivalents present should be essentially on a molar basis correspond to the total glycol equivalents present.
• Dicarboxylic acids suitable as component B) of the copolyester are e.g. malonic, Adipic, Azelaic, Glutaric, Sebacic, Cork, Bemstein and Brassylic acid as well Mixtures of these acids or their derivatives capable of forming polyester. Of the acids mentioned, sebacic acid is preferred.
• sulfomonomers which contain a metal sulfonate group on the aromatic part of an aromatic dicarboxylic acid (component C) are those monomers which correspond to the following general formula: In this formula is M is a monovalent cation of an alkali metal, Z is a trivalent aromatic radical, and X and Y are carboxyl groups or polyester-forming equivalents.
• Monomers of this type are described in US-A 3,563,942 and 3,779,993.
• Examples of such monomers are sodium sulphoterephthalic acid, sodium 5-sulphoisophthalic acid, sodium sulphophthalic acid, 5- (p-sodium sulphphenoxy) isophthalic acid, 5- (sodium sulphopropoxy) isophthalic acid and the like monomers as well as their derivatives capable of forming polyesters, e.g. the dimethyl esters.
• M is preferably Na + , Li + or K + .
• Glycols suitable as component D) are e.g. Ethylene glycol, 1,5-pentadiol, 1,6-hexanediol, Neopentyl glycol, 1,10-decanediol, cyclohexane-dimethanol and the like Substances.
• Ethylene glycol is preferably used.
• the copolyesters can be made by known polymerization techniques. The general procedure is to bring the acid components together with glycol and heated in the presence of an esterification catalyst then adding a polycondensation catalyst.
• the target amount is within the specified range preferably 1 to 20 mol%, based on the acid components of the mixture II, if component B is contained in the composition.
• the glycol component is present in a stoichiometric amount.
• copolyesters suitable for the purposes of the invention continue to stand out characterized in that they have an acid number below 10, preferably from 0 to 3, an average Mole weight below about 50,000 and SV in the range of about 30 to 700, preferably about 350 to 650.
• the film contains a UV stabilizer and a flame retardant.
• the UV stabilizer is expediently so-called masterbatch technology is metered directly during film production, the concentration of the UV stabilizer is preferably between 0.01% by weight and 5% by weight, based on the weight of the layer of crystallizable thermoplastic is.
• the flame retardant is also according to the invention via the so-called Masterbatch technology metered in directly during film production, with the Concentration between 0.5 and 30% by weight, preferably between 1 and 20% by weight, based on the weight of the layer of crystallizable thermoplastic.
• thermoplastics especially the ultraviolet portion of solar radiation, i.e. H. the wavelength range from 280 to 400 nm, initiates degradation processes as thermoplastics Do not just follow the visual appearance due to color change or Yellowing changes, but also the mechanical-physical properties negative to be influenced.
• Polyethylene terephthalates for example, start below 360 nm UV light to absorb, their absorption increases considerably below 320 nm and is very pronounced below 300 nm. The maximum absorption is between 280 and 300 nm.
• the photooxidation of polyethylene terephthalates can also take place via hydrogen elimination in the ⁇ -position of the ester groups to form hydroperoxides and their decomposition products as well as related chain splits (H. Day, D. M. Wiles: J. Appl. Polym. Sci 16, 1972, page 203).
• UV stabilizers or UV absorbers as light stabilizers are chemical compounds, into the physical and chemical processes of light-induced degradation can intervene. Soot and other pigments can partially protect against light cause. However, these substances are unsuitable for transparent films because they are used for Discoloration or color change. For transparent, matt films are only organic and organometallic compounds suitable to the stabilized Do not impart any or only an extremely slight color or color change to thermoplastics, d. H. which are soluble in the thermoplastic.
• UV stabilizers suitable as light stabilizers for the purposes of the present invention are UV stabilizers which absorb at least 70%, preferably 80%, particularly preferably 90%, of the UV light in the wavelength range from 180 nm to 380 nm, preferably 280 to 350 nm. These are particularly suitable if they are thermally stable in the temperature range from 260 to 300 ° C, ie do not decompose and do not lead to outgassing.
• Suitable UV stabilizers as light stabilizers are, for example, 2-hydroxybenzophenones, 2-hydroxybenzotriazoles, organo-nickel compounds, salicylic acid esters, cinnamic acid ester derivatives, resorcinol monobenzoates, oxalic acid anilides, hydroxybenzoic acid esters, sterically hindered amines and triazines, the 2-hydroxybenzotriazoles being preferred.
• the film according to the invention contains at least one flame retardant which is metered in directly during film production using the so-called masterbatch technology, the concentration of the flame retardant being in the range from 0.5 to 30.0% by weight, preferably from 1.0 to 20.0 wt .-%, based on the weight of the layer of crystallizable thermoplastic, is.
• a ratio of flame retardant to thermoplastic in the range from 60 to 40% by weight to 10 to 90% by weight is generally maintained in the production of the masterbatch.
• Typical flame retardants include bromine compounds, chlorinated paraffins and other chlorine compounds, antimony trioxide, aluminum trihydrates, the halogen compounds disadvantageous due to the resulting halogen-containing by-products are. Furthermore, the low light resistance of a film equipped with it in addition to the development of hydrogen halide in the event of fire extremely disadvantageous.
• Suitable flame retardants which are used according to the invention are organic phosphorus compounds such as carboxyphosphinic acids and their Anhydrides. It is essential to the invention that the organic phosphorus compound is soluble in the thermoplastic, otherwise the required optical properties are not met.
• hydrolysis stabilizer Since the flame retardants generally have a certain sensitivity to hydrolysis have, the additional use of a hydrolysis stabilizer may be useful.
• Phenolic stabilizers alkali / alkaline earth stearates are generally used as hydrolysis stabilizers and / or alkali / alkaline earth carbonates in amounts of 0.01 to 1.0% by weight used. Phenolic stabilizers are used in an amount of 0.05 to 0.6% by weight, in particular 0.15 to 0.3 wt .-% and with a molecular weight of more than 500 g / mol prefers.
• the film according to the invention contains, in addition to 1% by weight to 20% by weight of a flame retardant, 0.01% by weight to 5.0% by weight of 2- (4,6-diphenyl- 1,3,5-triazin-2-yl) -5- (hexyl) oxyphenol of the formula or 0.01% to 5.0% by weight of 2,2-methylene-bis (6- (2H-benzotriazol-2-yl) -4- (1,1,2,2-tetramethylpropyl) - phenol of the formula
• mixtures of these two UV stabilizers or mixtures of at least one of these two UV stabilizers with other UV stabilizers can also be used, the total concentration of light stabilizers preferably being between 0.01% by weight and 5.0% by weight. -%, based on the weight of crystallizable polyethylene terephthalate; lies.
• the base layer and / or the cover layer (s) can, in addition to the UV stabilizer and the flame retardant added using masterbatch technology Contain additives such as stabilizers and antiblocking agents. You will be expedient to that Polymer or the polymer mixture added before melting.
• Stabilizers are, for example, phosphorus compounds, such as phosphoric acid or Phosphoric acid ester used.
• Typical antiblocking agents are inorganic and / or organic particles, for example calcium carbonate, amorphous silica, talc, magnesium carbonate, Barium carbonate, calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, Magnesium phosphate, aluminum oxide, lithium fluoride, calcium, barium, zinc or Manganese salts of the dicarboxylic acids used, carbon black, titanium dioxide, or kaolin cross-linked polymer particles such as polystyrene or acrylate particles.
• the particles can be the individual Layers in the usual concentrations, e.g. as a glycolic dispersion during the Polycondensation or masterbatches can be added during extrusion.
• pigment concentrations 0.0001 to 10% by weight have been particularly suitable proved.
• By adding these particles to the top layer you have one Another advantageous way to vary the degree of matting of the film. With the increase the pigment concentration is usually an increase in the degree of mattness of the film connected.
• a detailed description of the antiblocking agents can be found, for example in EP A 0 602 964.
• the masterbatch which contains the flame retardant and optionally contains the hydrolysis stabilizer, pre-crystallized or pre-dried becomes.
• This predrying involves gradual heating of the masterbatch reduced pressure (20 to 80 mbar, preferably 30 to 60 mbar, in particular 40 to 50 mbar) and with stirring and, if necessary, drying at constant, elevated temperature also under reduced pressure.
• the masterbatch will preferably at room temperature from a dosing container in the desired one Mixing together with the polymers of the base and / or cover layers and If necessary, other raw material components in batches in a vacuum dryer, which in the Temperature range from 10 ° C to 160 ° C during the drying or dwell time, preferably 20 ° C to 150 ° C, in particular 30 ° C to 130 ° C passes.
• Residence time is the raw material mixture with 10 to 70 rpm, preferably 15 to 65 rpm, in particular stirred 20 to 60 rpm.
• the so pre-crystallized or pre-dried Raw material mix is in a downstream, also evacuated container at 90 ° to 180 ° C, preferably 100 ° C to 170 ° C, especially 110 ° C to 160 ° C for 2 up to 8 hours, preferably 3 to 7 hours, in particular 4 to 6 hours dried.
• Granules are expediently used to produce the top layer according to the invention from mixture component I and granules from mixture component II in desired mixing ratio and, if necessary, the flame retardant masterbatch, which is pre-dried is fed directly to the extruder. It turned out to be Proven useful for the extrusion of the matt top layer according to the invention to use a twin screw extruder, e.g. in EP 0 826 478 is described.
• the materials can be at about 300 ° C and with a residence time melt and extrude for about 5 minutes. Under these conditions, Extruder transesterification reactions take place, in which further copolymers from the Homopolymers and the copolymers can form.
• the polymers for the base layer as well as the flame retardant masterbatch, which is predried, are expediently fed via a further extruder. Approximately Existing foreign bodies or impurities can be removed from the polymer melt Filter off before extrusion.
• the melts are then in a multi-layer die formed into flat melt films and layered on top of each other. Subsequently the multilayer film with the help of a cooling roller and optionally other rollers peeled and solidified.
• Biaxial stretching is generally carried out sequentially or simultaneously. With sequential stretching, it is preferably only in the longitudinal direction (i.e. in Machine direction) and then in the transverse direction (i.e. perpendicular to the machine direction) stretched. This leads to an orientation of the molecular chains.
• the stretching in the longitudinal direction with the help of two according to the desired Carry out stretch ratio of rolls running at different speeds.
• transverse stretching one generally uses an appropriate tenter frame.
• the film is simultaneously in the longitudinal and transverse directions in one Tenter frame stretched.
• the temperature at which the drawing is carried out can be in a relative vary widely and depends on the desired properties of the Foil.
• the aspect ratio is generally in the range from 2.5: 1 to 6: 1, preferably from 3: 1 to 5.5: 1.
• the transverse stretching ratio is general in the range from 3.0: 1 to 5.0: 1, preferably from 3.5: 1 to 4.5: 1. If desired, can a longitudinal stretching and even another stretching at the transverse stretching Connect transverse stretching.
• the film In the subsequent heat setting, the film is held at about 0.1 to 10 s Temperature kept from 150 to 250 ° C. Then the film in the usual way wound.
• the film can also be coated on at least one of its surfaces, so that the coating on the finished film has a thickness of 5 to 100 nm, preferably 20 to 70 nm, in particular 30 to 50 nm. Coating is preferred Applied in-line, i.e. during the film manufacturing process, advantageously before the transverse stretch. Application by means of "reverse” is particularly preferred gravure-roll coating "process, in which the coatings are extremely homogeneous Apply in the layer thicknesses mentioned.
• the coatings are preferably applied as solutions, suspensions or dispersions, especially preferably as an aqueous solution, suspension or dispersion.
• Coatings give the film surface an additional function, for example the film is sealable, printable, metallizable, sterilizable, antistatic or improve e.g. the flavor barrier or allow adhesion to materials that otherwise would not adhere to the film surface (e.g. photographic emulsions).
• the film is sealable, printable, metallizable, sterilizable, antistatic or improve e.g. the flavor barrier or allow adhesion to materials that otherwise would not adhere to the film surface (e.g. photographic emulsions).
• substances / compositions that have additional functionality lend are:
• the substances / compositions mentioned are a dilute solution, emulsion or dispersion preferably as an aqueous solution, emulsion or dispersion on a or applied both film surfaces and then the solvent volatilized. If the coatings are applied in-line before transverse stretching, Usually the temperature treatment in the transverse stretching and subsequent is sufficient Heat fixation to volatilize the solvent and the coating too dry. The dried coatings then have those previously mentioned desired layer thicknesses.
• the films can be coated, preferably in an off-line process, with metals such as aluminum or ceramic materials such as SiO x or Al x O y . This improves their gas barrier properties in particular.
• the polyester film according to the invention preferably also contains a second one Top layer C.
• Structure, thickness and composition of a second top layer can be selected independently of the existing top layer, whereby the second top layer also the polymers already mentioned, the UV stabilizer, the flame retardant or polymer mixtures for the base or the invention may contain the first cover layer, but not with that of the first Top layer must be identical.
• the second top layer can also be other common Top layer polymers also contain the UV stabilizer and / or the flame retardant can be equipped.
• an intermediate layer there may still be between the base layer and the cover layer (s) an intermediate layer. It can be made from those described for the base layers Polymers exist. In a particularly preferred embodiment, it consists of the polyester used for the base layer. You can also use the ones described contain conventional additives and the flame retardant and / or the UV stabilizer.
• the thickness of the intermediate layer is generally greater than 0.3 ⁇ m and lies preferably in the range from 0.5 to 15 ⁇ m, in particular 1.0 to 10 ⁇ m.
• the thickness of the cover layer (s) is generally greater than 0.1 ⁇ m and lies preferably in the range from 0.2 to 5 ⁇ m, in particular 0.2 to 4 ⁇ m, the Cover layers can be of the same or different thickness.
• the total thickness of the polyester film according to the invention can be within wide limits vary and depends on the intended use. It is preferably 4 to 500 ⁇ m, in particular 5 to 450 ⁇ m, preferably 6 to 300 ⁇ m, wherein the base layer is preferably about 40 to 90% of the Total thickness.
• the film according to the invention can be easily recycled without polluting the environment, making them suitable for use as short-lived advertising signs, for example Exhibition stand construction and for other short-lived promotional items, where fire protection and UV absorption is desired.
• the manufacturing cost of the invention Film is only slightly above that of a film made of standard polyester raw materials.
• the other processing and use-relevant properties of the invention Films remain essentially unchanged or are even improved.
• the production of the film ensures that the regrind is in one Proportion of up to 50% by weight, preferably 10 to 50% by weight, in each case based on the Total weight of the film, can be reused without losing the physical Properties of the film are significantly negatively affected.
• the film according to the invention is characterized by its low flammability according to DIN 4102 (building material class B1 and B2), UV light impermeability, high UV stability, low gloss, especially low Gloss of the film surface A, and from a comparatively low haze. It also has good winding and processing behavior. Furthermore is worth mentioning that the top layer according to the invention works well with ballpoint pens, Felt-tip pen or fountain pen can be labeled.
• the gloss of the film surface A is less than 70. In a preferred embodiment the gloss of this side is less than 60 and in one particular preferred embodiment less than 50. This film surface thus conveys a particularly high advertising character.
• the film also fulfills building material classes B1 and B2 according to DIN 4102 part 1 and part 2 and shows no embrittlement when exposed to temperature. Compared to one Standard film does not increase the yellowness index (YID) of the film according to the invention.
• the Film only allows light or radiation of> 360 nm to pass through, ie. H. the film absorbs the harmful UV radiation.
• the haze of the film according to the invention is less than 40%. In a preferred one In one embodiment, the haze of the film is less than 35% and in one particularly preferred embodiment less than 30%.
• the film e.g. can be printed in reverse printing or viewing windows can be installed, e.g. the contents can be seen very well.
• the combination of excellent properties makes the invention suitable Film excellent for a variety of different applications, for example for interior cladding, for exhibition stand construction and exhibition items, as displays, for Signs, for protective glazing of machines and vehicles, in the lighting sector, in shop and shelf construction, as promotional items, laminating medium, for greenhouses, Canopies, external cladding, covers, applications in Construction sector and illuminated advertising profiles, shadow mats, electrical applications.
• Label as a release film or as an embossing film or in-mold labeling.
• Table 1 summarizes the most important film properties according to the invention.
• area according to the invention prefers particularly preferred unit Measurement Method Gloss, side A (Measuring angle 60) ⁇ 70 ⁇ 60 ⁇ 50 DIN 67 530 cloudiness ⁇ 40 ⁇ 35 ⁇ 30 % ASTM-D Coefficient of friction: DIN 53 375 A side against itself C or ⁇ 0.6 ⁇ 0.55 ⁇ 0.50 B side against yourself ⁇ 0.5 ⁇ 0.55 ⁇ 0.55 average roughness R, (A-side) 200-600 230-550 250 - 530 nm DIN 4768, with a cut-off of 0.25 nm Yellowness Index (YID) ⁇ 30 ⁇ 20 ⁇ 10 DIN 6167 High UV stability UV light transmission from wavelength > 350 > 360 > 370 nm Building material class according to DIN 4102 Part 2 and Tell 1 fulfills B 2 meets B 1
• YID Yellowness Index
• the standard viscosity SV (DCE) is measured based on DIN 53726 in dichloroacetic acid.
• the friction was determined in accordance with DIN 53 375.
• the sliding friction number was 14 days measured after production.
• the surface tension was measured using the so-called ink method (DIN 53 364) certainly.
• the haze of the film was measured according to ASTM-D 1003-52.
• the turbidity measurement according to Hölz was determined on the basis of ASTM-D 1003-52, but using Utilization of the optimal measuring range on four superimposed foil layers measured and a 1 ° slit was used instead of a 4 ° pinhole.
• the gloss was determined in accordance with DIN 67 530.
• the reflector value was measured as optical parameter for the surface of a film. Based on the standards ASTM-D 523-78 and ISO 2813 the angle of incidence was set at 20 ° or 60 °. On The light beam strikes the flat test surface and at the set angle of incidence is reflected or scattered by it. The on the photoelectronic receiver striking light rays are displayed as a proportional electrical quantity. The The measured value is dimensionless and must be specified with the angle of incidence.
• the roughness R a of the film was determined according to DIN 4768 with a cut-off of 0.25 mm.
• the modulus of elasticity and the tensile strength and elongation at break are in longitudinal and Transverse direction measured according to ISO 527-1-2.
• the UV stability is tested according to the test specification ISO 4892 as follows tester Atlas Ci 65 Weather Ometer test conditions ISO 4892, ie artificial weathering exposure time 1000 hours (per page) radiotherapy 0.5 W / m 2 , 340 nm temperature 63 ° C Relative humidity 50% Xenon lamp inner and outer filter made of borosilicate irradiation cycles 102 minutes of UV light, then 18 minutes of UV light with water spraying the samples, then again 102 minutes of UV light, etc.
• the yellowness index (YID) is the deviation from the colorlessness in the direction of "yellow” and is measured according to DIN 6167. Yellow values (YID) of ⁇ 5 are not visible.
• the following examples and comparative examples are each transparent foils of different thickness on the extrusion line described getting produced.
• the pre-dried flame retardant is dosed into the base layer in the form of a master batch.
• the flame retardant masterbatch consists of 20% by weight of flame retardant and 80% by weight of polyester
• the flame retardant is the organic one that is soluble in polyester Phosphor compound® Amgard P1045 from Albright & Wilson.
• the base layer has the following composition: 75% by weight Polyethylene terephthalate (RT49 from Hoechst AG) with an SV value of 800 and 5% by weight Masterbatch made of 99% by weight of polyethylene terephthalate and 1.0% by weight of silica particles (® Sylobloc 44 H from Grace) with an average particle size of 4.5 ⁇ m 20% by weight of the flame retardant masterbatch.
• RT49 Polyethylene terephthalate
• Masterbatch made of 99% by weight of polyethylene terephthalate and 1.0% by weight of silica particles (® Sylobloc 44 H from Grace) with an average particle size of 4.5 ⁇ m 20% by weight of the flame retardant masterbatch.
• the components of the base layer are separated at room temperature Dosing containers filled in a vacuum dryer, which before the filling time At the end of the dwell time, a temperature range of 25 ° C to 130 ° C passes.
• the raw material mixture is stirred at 61 rpm during the 4-hour residence time.
• the pre-crystallized or pre-dried raw material mixture is in the downstream Hopper also under vacuum at 140 ° C for 4 hours dried and fed to the extruder for the base layer.
• Chips of polyethylene terephthalate and a filler were also fed to the extruder for the cover layer C.
• a transparent three-layer film with ABC structure and a total thickness of 12 ⁇ m was then produced by coextrusion and subsequent stepwise orientation in the longitudinal and transverse directions.
• the cover layers each had a thickness of 1.5 ⁇ m.
• Top layer A 75% by weight Component I 15% by weight Component II and 10% by weight UV masterbatch (5% by weight ® TINUVIN 1577, 95% by weight polyester)
• Top layer C 80% by weight Polyethylene terephthalate (RT49 from Hoechst AG) with an SV value of 800 and 10% by weight Masterbatch made from 99% by weight of polyethylene terephthalate and 1.0% by weight of silica particles (®Sylobloc 44 H from Grace) with an average particle size of 4.5 ⁇ m.
• 10% by weight UV masterbatch 5% by weight ® TINUVIN 1577, 95% by weight polyester
• Top layer A 70% by weight Component I 20% by weight Component II and 10% by weight UV masterbatch.
• top layer A was composed as follows: 55% by weight Component I 35% by weight Component II and 10% by weight UV masterbatch
• a monofilm was produced which, like cover layer A from example 3 was composed.
• the film surfaces had the required mattness, the film did not meet the requirements because it was too cloudy. Moreover it was very difficult to process the film reliably and therefore economically.
• the film is not UV stable and allows the harmful UV light to pass through. After 1000 hours of weathering, the film shows cracks and embrittlement signs as well as a visible yellowing.
• the film does not meet building material classes B1 and B 2.

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• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Laminated Bodies (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2000
  • 2000-01-20 DE DE10002160A patent/DE10002160A1/de not_active Withdrawn
• 2001
  • 2001-01-10 US US10/181,509 patent/US6730406B2/en not_active Expired - Fee Related
  • 2001-01-10 JP JP2001553119A patent/JP2003524541A/ja not_active Withdrawn
  • 2001-01-10 DE DE50101767T patent/DE50101767D1/de not_active Expired - Fee Related
  • 2001-01-10 EP EP01942596A patent/EP1261481B1/de not_active Expired - Lifetime
  • 2001-01-10 KR KR1020027009074A patent/KR20020065926A/ko not_active Withdrawn
  • 2001-01-10 WO PCT/EP2001/000211 patent/WO2001053089A1/de not_active Ceased

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